Substrate processing apparatus and method of confirming operation of liquid flowrate control device

ABSTRACT

A substrate processing apparatus and a method of confirming operation of a liquid flowrate control device. The apparatus includes a process chamber accommodating a substrate, a liquid source supply system supplying a liquid source into the chamber at a liquid state at room temperature and under atmospheric pressure, a solvent supply system supplying a solvent into the chamber having a vapor pressure greater than the liquid source, a liquid flowrate control device controlling flowrates of the liquid and solvent, and a controller controlling the liquid and solvent supply systems, and the liquid flowrate control device. The controller controls the liquid and solvent supply systems, and the liquid flowrate control device so the solvent is supplied to the liquid flowrate control device to check an operation of the liquid flowrate control device before the liquid source supply system supplies the liquid into the chamber via the liquid flowrate control device.

CROSS-REFERENCE TO RELATED PATENT APPLICATION

The present application is a Divisional Application of application Ser.No. 12/850,863, filed Aug. 5, 2010; which claims priority under 35U.S.C. §119 of Japanese Patent Application Nos. 2009-185110, filed onAugust 7, and 2010-157482, filed on Jul. 12, 2010, in the JapanesePatent Office, the entire contents of which are hereby incorporated byreference.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to a substrate processing apparatus, amethod of manufacturing a semiconductor device, and a method ofconfirming an operation of a liquid flowrate control device, which areadapted to manufacture a semiconductor device by performing processessuch as a thin film forming process, an oxidation process, an impuritydiffusion process, an annealing process, and an etching process on asubstrate such as a silicon wafer.

2. Description of the Related Art

In a substrate processing process, a liquid mass flow controller and avaporizer are used to perform a film forming process in which a liquidsource is supplied while vaporizing to form a thin film on a substrate.For example, when a zirconium oxide film is formed, tetrakis ethylmethylamino zirconium (TEMAZ) is used as a Zr source and ozone (O₃) is used asan oxygen source. However, TEMAZ is a liquid at ordinary temperaturesand pressures (room temperature), and is supplied into the vaporizer bythe control of the liquid mass flow controller. Then, the TEMAZ isvaporized in a vaporizer chamber inside the vaporizer to supply thevaporized TEMAZ gas together with an inert gas of a carrier into areaction chamber as gas.

Among substrate processing apparatuses, in a batch type apparatus inwhich fifty sheets to hundred fifty sheets of substrate are processed atone time, it is necessary to supply a relatively large amount of TEMAZ.As a method for supplying a large amount of gas, a source tank itselfmay be heated to increase a vapor pressure. However, since the TEMAZ isa material that can be easily thermal-decomposed, it is difficult toheat the source tank for a long time. In addition, since the TEMAZ is aliquid having a low vapor pressure, it is difficult to obtain asufficient flowrate using only its own vapor pressure without heating.

As a result, the TEMAZ is used through a method using the vaporizer inwhich the TEMAZ is in a liquid state at room temperature within thesource tank and is vaporized by heat only in the vaporizer.

In such a TEMAZ supply system, a solvent supply system is provided also.When a line member through which the liquid TEMAZ passes is replaced,since the TEMAZ has a low vapor pressure, it is actually impossible toremove the source using only vacuum exhaust and N₂ purge. Thus, asolvent having a vapor pressure greater than that of the TEMAZ eventhough it is in a liquid state at room temperature, for example, normalhexane (n-Hexane) flows to downwash the TEMAZ, thereby performing a linecleaning process. The n-Hexane does not react with the TEMAZ and meltsthe TEMAZ. In addition, the n-Hexane is easily evaporated because itdoes not react with components of the atmosphere.

FIG. 6 is a graph illustrating a saturated vapor pressure curve of TEMAZand n-Hexane. The TEMAZ has 0.004 Torr at a temperature of 30° C., andthe n-Hexane has about 180 Torr at a temperature of 30° C. As a result,it may be seen that the TEMAZ and the n-Hexane have a four-digit or morevapor pressure difference therebetween.

In a related art substrate processing apparatus, when a liquid mass flowcontroller is used firstly (including also when the liquid mass flowcontroller is used firstly after being replaced), it is necessary toconfirm an operation state of the liquid mass flow controller in a statewhere the liquid mass flow controller is installed in a batch typeapparatus. However, for confirming the operation state of the liquidmass flow controller, when the TEMAZ as a source flows actually, in casewhere non-restorable defects exist in the liquid mass flow controller,the liquid mass flow controller should be replaced. In addition, sinceprocesses such as a liquid removal process→a purge process→a cleaningprocess using the solvent→a purge process are required, it takes a longwork time.

Also, although the cleaning process is performed with a sufficient timeand a deliberate sequence, since there is a chance that a slight amountof liquid remains, it may be possible that the pipe may be contaminatedby the reaction between atmosphere and the residual source duringreplacement works.

SUMMARY OF THE INVENTION

An object of the present invention is to provide a substrate processingapparatus in which an operation of a liquid flowrate control device isconfirmed using a high volatile solvent having a high vapor pressurewhen the liquid flowrate control device is initially adjusted, andprocesses required in case where defects of the liquid flowrate controldevice are detected are reduced, and simultaneously, contamination dueto the residual liquid source is prevented, a method of manufacturing asemiconductor device, and a method of confirming the operation of theliquid flowrate control device.

According to an aspect of the present invention, there is provided asubstrate processing apparatus comprising: a process chamberaccommodating a substrate; a liquid source supply system supplying aliquid source into the process chamber, the liquid source being at aliquid state at room temperature and under atmospheric pressure; asolvent supply system supplying a solvent into the process chamber, thesolvent having a vapor pressure greater than that of the liquid source;a liquid flowrate control device controlling flowrates of the liquidsource and the solvent; and a controller controlling the liquid sourcesupply system, the solvent supply system, and the liquid flowratecontrol device, wherein the controller controls the liquid source supplysystem, the solvent supply system, and the liquid flowrate controldevice in a manner that the solvent is supplied to the liquid flowratecontrol device to check an operation of the liquid flowrate controldevice before the liquid source supply system supplies the liquid sourceinto the process chamber via the liquid flowrate control device.

According to another aspect of the present invention, there is provideda method of confirming an operation of a liquid flowrate control device,the method comprising: supplying a solvent into a liquid flowratecontrol device connected to a process chamber; monitoring the liquidflowrate control device to measure a flowrate of the solvent flowinginto the liquid flowrate control device; comparing the measured flowrateof the solvent to a threshold value; and removing the solvent from theprocess chamber when the flowrate of the solvent is within a range ofthe threshold value.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a schematic perspective view of a substrate processingapparatus according to the present invention.

FIG. 2 is a longitudinal sectional view of a process furnace accordingto the present invention.

FIG. 3 is a perspective view taken along line A-A of FIG. 2.

FIG. 4 is schematic configuration view illustrating a supply/exhaustsystem of a liquid source and solvent according to the presentinvention.

FIG. 5 is a flowchart illustrating a process for confirming an operationof a liquid flowrate control device according to the present invention.

FIG. 6 is a graph illustrating a saturated vapor pressure curve of theTEMAZ and n-Hexane.

FIG. 7 is a flowchart of a substrate processing process according to thepresent invention.

FIG. 8 is a sequence diagram illustrating a cycle of a film formingprocess of a substrate according to the present invention.

FIG. 9 is a block diagram illustrating a controller a substrateprocessing apparatus according to the present invention.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

Preferable embodiments of the present invention will be describedhereinafter with reference to the attached drawings.

First, with reference to FIG. 1, a substrate processing apparatus 1according to an embodiment of the present invention will be described.

The substrate processing apparatus 1 of the present invention, in whichcassettes 3 are used as wafer carriers for accommodating wafers(substrates) 2 made of a material such as silicon, includes a housing 4.A front maintenance entrance (not shown) is formed in the lower side ofa front wall 5 of the housing 4 as an opening for maintenance works, anda front maintenance door (not shown) is vertically installed to open andclose the front maintenance entrance. A cassette carrying port(substrate container carrying port) (not shown) is formed in the frontmaintenance door so as to communicate with the inside and outside of thehousing 4. At the inside of the cassette carrying port of the housing 4,a cassette stage (substrate container stage) 6 is installed. Thecassettes 3 are carried onto the cassette stage 6 and carried away fromthe cassette stage 6, by an in-process carrying device (not shown).

On the cassette state 6, by the in-process carrying device, the wafers 2inside the cassette 3 are vertically positioned, and a wafer takingin/out entrance of the cassette 3 is placed facing upward. The cassettestage 6 is configured so that the cassette 3 is rotated by 90°counterclockwise in a longitudinal direction toward the backward of thehousing 4, the wafers 2 inside the cassette 3 are horizontallypositioned, and the wafer taking in/out entrance of the cassette 4 facesthe backward of the housing 4.

At an approximately central part of the housing 4 in a front-to-backdirection, a cassette shelf (substrate container shelf) 7 is installed.The cassette shelf 7 is configured so that the plurality of cassettes 3is stored in a plurality of stages and a plurality of rows. At thecassette shelf 7, a transfer shelf 9 is installed to store the cassette3, which is a carrying object of a wafer transfer mechanism (describedlater) 8. Also, at the upside of the cassette stage 6, a standbycassette shelf 11 is installed to store standby cassettes 3.

Between the cassette stage 6 and the cassette shelf 7, a cassettecarrying device (substrate container carrying device) 12 is installed.The cassette carrying device 12 is configured by a cassette elevator(substrate container elevating mechanism) 13, which is capable of movingupward and downward while holding the cassette 3 and a cassette carryingmechanism (substrate container carrying mechanism) 14 as a carryingmechanism. By continuous motions of the cassette elevator 13 and thecassette carrying mechanism 14, the cassette carrying device 12 isdesigned to carry the cassette 3 among the cassette stage 6, thecassette shelf 7, and the standby cassette shelf 11.

At the backside of the cassette shelf 7, the wafer transfer mechanism(substrate transfer mechanism) 8 is installed. The wafer transfermechanism 8 is configured by a wafer transfer device (substrate transferdevice) 15 that is capable of rotating or linearly moving the wafer 2 ina horizontal direction and a wafer transfer device elevator (substratetransfer device elevating mechanism) 16 for moving the wafer transferdevice 15 upward or downward. By continuous motions of the wafertransfer device 15 and the wafer transfer device elevator 16, the wafer2 is picked by tweezers (substrate holder) 17 of the wafer transferdevice 15 and is charged into a boat (substrate holding tool) 18 anddischarged from the boat 18.

At the upside of the rear part of the housing 4, a process furnace 19 isinstalled.

The lower end part of the process furnace 19 is configured so as to beopened and closed by a furnace port shutter (furnace portopening/closing mechanism) 21.

At the downside of the process furnace 19, a boat elevator (substrateholding tool elevating mechanism) 22 is installed to move the boat 18upward to and downward from the process furnace 19. At an arm 23 as aconnecting unit connected to an elevating table of the boat elevator 22,a seal cap 24 as a cover part is horizontally installed. The seal cap 24vertically supports the boat 18 and is configured to block the lower endpart of the process furnace 19.

The boat 18 includes a plurality of holding members and is configured tohorizontally hold a plurality of wafers (for example, about fifty to onehundred fifty wafers) in a state where the centers of the wafers 2 arealigned and arranged in a vertical direction.

At the upside of the cassette shelf 7, a cleaning unit 25 configured bya supply fan and a dust filter is installed to supply clean air aspurified atmosphere, so that the clean air may flow inside of thehousing 4.

Also, at the left side end part of the housing 4 opposite to the wafertransfer device elevator 16 and the boat elevator 22, another cleaningunit (not shown) configured by a supply fan and a dust filter isinstalled to supply clean air. Thus, the clean air is blown from thecleaning unit (not shown) to the wafer transfer device 15 and the boat18, and after passing through the wafer transfer device 15 and the boat18, the clean air is sucked by an exhaust device (not shown) anddischarged to the outside of the housing 4.

Next, an operation of the substrate processing apparatus 1 will bedescribed.

The cassette 3 is placed on the cassette stage 6 through a cassettecarrying port (not shown) in a state where the wafers are verticallypositioned in the cassette 3 and the wafer taking in/out entrance of thecassette 3 faces upward. Thereafter, the cassette 3 is rotated 90°counterclockwise in a longitudinal direction toward the backward of thehousing 4 by the cassette state 6 so that the wafers 2 inside thecassette 3 are horizontally positioned and the wafer taking in/outentrance of the cassette 3 faces the backward of the housing 4.

Next, the cassette 3 is automatically carried and placed by the cassettecarrying device 12 to a specified shelf position of the cassette shelf 7or the standby cassette shelf 11 so as to be temporarily stored, andthen transferred from the cassette shelf 7 or the standby cassette shelf11 to the transfer shelf 9 by the cassette carrying device 12, ordirectly transferred to the transfer shelf 9.

After the cassette 3 is transferred to the transfer shelf 9, the wafer 2is picked up from the cassette 3 through the wafer taking in/outentrance and is charged into the boat 18 disposed at the backward of thetransfer shelf 9 by the tweezers 17 of the wafer transfer device 15.After delivering the wafer 2 to the boat 18, the wafer transfer device15 returns to the cassette 3, and then charges the next wafer 2 into theboat 18.

After a predetermined number of wafers 2 is charged into the boat 18,the lower end of the process furnace 19 closed by the furnace portshutter 21 is opened by moving the furnace port shutter 21.Subsequently, the boat 18 holding the wafers 2 is loaded into theprocess furnace 19 by lifting the seal cap 24 using the boat elevator22. After the loading, a predetermined heat treatment is performed onthe wafers 2 inside the process furnace 19. Thereafter, the wafers 2 andthe cassette 3 are carried out to the outside of the housing 4 in areverse sequence of the above.

Next, with reference to FIGS. 2 and 3, the process furnace 19 applied tothe substrate processing apparatus 1 will be described. Also, the samepart in FIGS. 2 and 3 as in FIG. 1 will be designated by the samereference numeral, and description thereof will be omitted.

Inside a heater 26 which is a heating device (heating unit), a reactiontube 27 as a reaction vessel is installed to process the wafers(substrates) 2. At the lower end of the reaction tube 27, for example, amanifold 28 made of stainless steel is installed, and at the lower endpart of the manifold 28, the seal cap 23 as a furnace port cap isinstalled. The seal cap 24 is, for example, a disk-shaped member made ofa metal such as stainless steel. On the top surface of the seal cap 24,an O-ring 29 is installed as a seal member that is in contact with thelower end of the manifold 28. The seal cap 24 air-tightly closes a lowerend opening of the manifold 28 by disposing the O-ring 29 therebetween.Also, a process chamber is constituted by at least the reaction tube 27,the manifold 28, and the seal cap 24.

At the seal cap 24, the boat 18 is erected by disposing the boat supportstand 32 between the seal cap 24 and the boat 18. The boat support stand32 is a holder which is used to hole the boat 18. The boat 18 isinserted in the process chamber 31. At the boat 18, a plurality ofwafers 2 to be batch-processed is held in a horizontal position and isvertically piled in multiple stages. Also, the heater 26 heats thewafers 2 inserted into the process chamber 31 to a predeterminedtemperature.

At the process chamber 31, a first gas supply pipe 33 and a second gassupply pipe 34 are installed as supply passages for supplying aplurality of processing gases (in the current embodiment, two kinds ofprocessing gases). At the first gas supply pipe 33, a liquid mass flowcontroller 35 which is a flowrate control device (flowrate controlunit), a vaporizer 36, and a first valve 37 which is an on/off valve aresequentially installed in an upstream direction, and a first carrier gassupply pipe 38 for supplying carrier gas is jointed with the first valve37. At the first carrier gas supply pipe 38, a second mass flowcontroller 39 which is a flowrate control device (flowrate control unit)and a third valve 41 which is an on/off valve are sequentially installedin an upstream direction.

Also, at the front end part of the first gas supply pipe 33, in anarc-shaped space between an inner wall of the reaction tube 27constituting the process chamber 31 and the wafers 2, a first nozzle 43is installed from a lower port to an upper part of the inner wall of thereaction tube 27 along the piled direction of the wafers 2. In a lateralsurface of the first nozzle 43, a first gas supply hole 44 for supplyinggas is formed. The first gas supply hole 44 has the same open area andis formed at the same pitch from the lower side to the upper side.Mainly, a first gas supply system (in case where a source materialsupplied from the first gas supply pipe 33 is liquid, a liquid sourcesupply system) is constituted by the first gas supply pipe 33, theliquid mass flow controller 35, the vaporizer 35, the first valve 37,and the first nozzle 43.

At the second gas supply pipe 34, a first mass flow controller 45 whichis a flowrate control device (flowrate control unit) and a second valve46 which is an on/off valve are sequentially installed in an upstreamdirection, and a second carrier gas supply pipe 47 for supplying carriergas is jointed with the second valve 46. At the second carrier gassupply pipe 47, a third mass flow controller 48 which is a flowratecontrol device (flowrate control unit) and a fourth valve 49 which is anon/off valve are sequentially installed in an upstream direction.

Also, at the front end part of the second gas supply pipe 34, in thearc-shaped space between the inner wall of the reaction tube 27constituting the process chamber 31 and the wafers 2, a second nozzle 51is installed from a lower port to an upper part of the inner wall of thereaction tube 27 along the piled direction of the wafers 2. In a lateralsurface of the second nozzle 51, a second gas supply hole 52 forsupplying gas is formed. The second gas supply hole 52 has the same openarea and is formed at the same pitch from the lower side to the upperside. Mainly, a second gas supply system (in case where reaction gasreacting with the source material is supplied, a reaction gas supplysystem) is constituted by the second gas supply pipe 34, the first massflow controller 45, the second valve 46, and the second nozzle 51.

For example, when a source material supplied from the first gas supplypipe 33 is liquid, the liquid mass flow controller 35, the vaporizer 36,and the first valve 37 are sequentially installed from the first gassupply pipe 33, and the first gas supply pipe 33 is jointed with thefirst carrier gas supply pipe 38, and furthermore, the first nozzle 43is installed therebetween to supply source gas into the process chamber31. For example, when a source material supplied from the first gassupply pipe 33 is gas, the liquid mass flow controller 35 is replacedwith a gas mass flow controller, and thus, the vaporizer 36 isunnecessary. Also, the first mass flow controller 45 and the secondvalve 46 are sequentially installed from the second gas supply pipe 34,and the second gas supply pipe 34 is joint with the second carrier gassupply pipe 47, and furthermore, the second nozzle 51 is installedtherebetween to supply the reaction gas reacting with the sourcematerial supplied from the first gas supply pipe 33 into the processchamber 31.

Also, at the process chamber 31, a gas exhaust pipe 53 is installed toexhaust the inside atmosphere of the process chamber 31. At the gasexhaust pipe 53, a pressure sensor 62 as a pressure detector (pressuredetecting unit) configured to regulate the inner pressure of the processchamber 31 is installed, and simultaneously, an auto pressure controller(APC) valve (fifth valve) 54 as a pressure regulator (pressureregulating unit) is installed and connected to a vacuum pump 55 which isan exhaust device (exhaust unit), so that the inside of the processchamber 31 is vacuum-evacuated to a predetermined pressure (vacuumdegree). The APC valve 54 is an on/off valve, which may be opened andclosed to stop the vacuum evacuation of the inside of the processchamber 31 and may adjust the inner pressure by adjusting a degree ofvalve opening. Mainly, an exhaust system is constituted by the gasexhaust pipe 53, the APC valve 54, the vacuum pump 55, and the pressuresensor 62.

Also, the arc-shaped space between the inner wall of the reaction tube27 inside the process chamber 31 and the wafers 2, an L-shapedtemperature sensor 63 is installed as a temperature detector extendingfrom a lower side of the reaction tube 27 along the inner wall of thereaction tube 27. Thus, based on temperature information detected by thetemperature sensor 63, the electrified state of the heater 26 iscontrolled in order that the inside of the process chamber 31 is made tohave a desired temperature distribution.

At the center part of the inside of the reaction tube 27, the boat 18 inwhich a plurality of wafers 2 are placed in multiple stages at the sameintervals is installed, and the boat 18 may be loaded into and unloadedfrom the reaction tube 27 by the boat elevator 22. Also, at the lowerside of the seal cap 24, a boat rotating mechanism 56 for rotating theboat 18 is installed to improve processing uniformity. A rotation shaft64 of the boat rotating mechanism 56 passes through the seal cap 24 andis connected to the lower end of the boat support stand 32, so that theboat 18 held on the boat support stand 32 may be rotated by rotating theboat rotating mechanism 56.

The controller 57, which is a control unit, is electrically connected tothe first to third mass flow controllers 45, 39, and 48, the first tofourth valves 37, 41, and 49, the APC valve 54, the heater 26, thevacuum pump 55, the boat rotating mechanism 56, the boat elevator 22,the pressure sensor 62, and the temperature sensor 63. Also, by thecontroller 57, flowrate adjusting operations of the liquid mass flowcontroller 35 and the first to third mass flow controllers 45, 39, and48; opening and closing operations of the first to fourth valves 37, 46,41, and 49; opening, closing, and pressure adjusting operations of theAPC valve 54; a temperature adjusting operation of the heater 26; startand stop operations of the vacuum pump 55; a rotation speed adjustingoperation of the boat rotating mechanism 56; and an elevating operationof the boat elevator 22 are controlled, and simultaneously, a flowratedetected by the liquid mass flow controller 35 and the first to thirdmass flow controllers 45, 39, and 48; a pressure inside the processchamber 31 detected by the pressure sensor 62; and a temperature insidethe process chamber 31 inside the process chamber 31 detected by thetemperature sensor 63 are regularly fed back.

As shown in FIG. 9, the controller 57 includes a measuring part whichmeasures the flowrate detected and fed back by the liquid mass flowcontroller 35, a memory in which a preset threshold is stored, and acomparing part which compares the measured value of the flowratemeasured by the measurement to the threshold stored in the memory.

In the process furnace 19 in of the current embodiment, a highdielectric constant (high-k) film such as a ZrO₂ or hafnium HFO₂ film isformed. As the reaction material (film forming material), the ZrO₂ filmmay be formed using reaction materials such as tetrakis ethylmethylamino zirconium (TEMAZ, Zr(NEtME)₄), Zr(O-tBu)₄, tetrakis dimethyl amidozirconium (TDMAZ, Zr(NMe2)₄), tetrakis diethyl amino zirconium (TEEAZ,Zr(NEt2)4) and the like. Also, the HfO₂ film may be formed usingreaction materials such as tetrakis ethyl methyl amino hafnium (TEMAH,Hf(NEtMe)₄), Hf(O-tBu)₄, Hf(NMe₂)₄, Hf(NEt₂)₄, Hf(MMP)₄ and the like.Here, Me represents a methyl group (CH₃), Et represents an ethyl group(C₂H₅), and Zr(O-tBu)₄ represents Zr(OC(CH₃)₃)₄.

In addition to the above materials, it is possible to use amine-compoundmaterials expressed by chemical formula Xn(NR¹R²)m (elements in III to Vfamilies, R1 and R2 indicate Me or Et, and n and m indicate naturalnumbers).

Hereinafter, an example of the film forming process using an atomiclayer deposition (ALD) method as a kind of a chemical vapor deposition(CVD) method will be described based on an example for forming the ZrO₂film using TRMAZ and O₃ which is one of manufacturing processes of asemiconductor device.

In the CVD method or the ALD method, for example, in the CVD method, aplurality of kinds of gases containing a plurality of elements thatconstitute a film to be formed are simultaneously supplied, and in theALD method, a plurality of kinds of gases containing a plurality ofelements that constitute a film to be formed are alternately supplied.Also, a silicon nitride film (SiN film) or a silicon oxide film (SiOfilm) is formed by controlling supply conditions such as the gasflowrates of the supply gases, the supply times of the supply gases, andplasma power. For example, in the case of forming the SiN film, thesupply conditions are controlled so as to adjust the composition ratioof the SiN film to the stoichiometric composition of N/Si≈1.33, and inthe case of forming the SiO film, the supply conditions are controlledso as to adjust the composition ratio of the SiO film to thestoichiometric composition of O/Si≈2.

In addition, the supply conditions may be controlled so that thecomposition ratio of the film to be formed is different from thestoichiometric composition. That is, the supply conditions may becontrolled so that at least one of a plurality of elements constitutingthe film to be formed is excessive in amount as compared with otherelements in terms of the stoichiometric composition. As described above,a process of forming a film may be performed while controlling the ratioof the plurality of elements constituting the film to be formed, thatis, the composition ratio of the film. Hereinafter, with reference to aflow chart of FIG. 7 and a sequence diagram of FIG. 8, a process offorming a ZrO₂ film by the ALD method will be described.

In the ALD method, for example, when the ZrO₂ film is formed, highquality films may be formed at a low temperature of 150° C. to 250° C.using TEMAH and O₃.

First, as described above, when the wafers 2 are charged into the boat18, as illustrated in FIG. 2, the boat 18 holding the wafers 2 is liftedby the boat elevator 22 and loaded into the process chamber 31. In thisstate, the seal cap 24 seals the lower end opening of the manifold 28 bydisposing the O-ring 29 therebetween.

Next, the inside of the process chamber 31 is vacuum-exhausted to adesired pressure (vacuum degree) by the vacuum pump 55. At this time,the pressure inside the process chamber 31 is measured by the pressuresensor 62, and the APC valve 54 is feed-back controlled (pressureadjustment) based upon the measured pressure. Also, the inside of theprocess chamber 31 is heated by the heater 26 in order that the insideof the process chamber 31 is made to have a desired temperaturedistribution. In this case, based upon temperature information detectedby the temperature sensor 63, the electrified state of the heater 26 isfed back. Subsequently, the boat 18 is rotated by the boat rotatingmechanism 56, and therefore, the wafers 2 are rotated. In this state,the TEMAZ gas and O₃ gas are supplied into the process chamber 31 toform the ZrO₂ film. In the film forming process, four steps illustratedin the sequence diagram of FIG. 8 are sequentially executed.

STEP: 01

Under the command of the controller 57, the TEMAZ flows into the firstgas supply pipe 33, and carrier gas (N₂) flows into the first carriergas supply pipe 38. At this time, the APC valve 54 of the gas exhaustpipe 53 is kept open.

Next, the first valve 37 and the third valve 41 are opened together. Thecarrier gas flows from the first carrier gas supply pipe 38, and aflowrate thereof is adjusted to a set value, which is set by thecontroller 57, by the second mass flow controller 39. The TEMAZ flowsfrom the first gas supply pipe 33, and a flowrate thereof is adjusted toa set value, which is set by the controller 57, by the liquid mass flowcontroller 35. Then, the TEMAZ is vaporized by the vaporizer 36, mixedwith carrier gas whose the flowrate is adjusted together, and themixture is supplied into the process chamber 31 from the first gassupply hole 44 while it is exhausted from the gas exhaust pipe 53.

At this time, by appropriately adjusting the APC valve 54, the inside ofthe process chamber 31 is maintained at a pressure in the range of 10 Pato 900 Pa, for example, 30 Pa. Also, a supply rate of the TEMAZcontrolled by the liquid mass flow controller 35 is 0.1 g/min to 0.5g/min. The wafers 2 are exposed to the TEMAZ gas for 1 second to 300seconds. At this time, the temperature of the heater 26 is set so thatthe wafer temperature is in a range of 150° C. to 250° C., for example,220° C. Then, by supplying the TEMAZ into the process chamber 31, asurface reaction (chemical adsorption) with a surface part such as anunder-layer film on the wafer 2 occurs.

STEP: 02

Next, the first valve 37 is closed, and the supply of TEMAZ is stopped.

In a state where the APC valve 54 is kept open, the gas is exhausted bythe vacuum pump 55 until the inside of the process chamber 31 reaches toa pressure of 20 Pa or less, and the remaining TEMAZ gas is exhaustedfrom the process chamber 31. At this time, when an inert gas such as N₂or the like is supplied into the process chamber 31, the effect foreliminating the remaining TEMAZ gas may be further enhanced.

STEP: 03

Next, the second valve 46 and the fourth valve 49 are opened together,and the carrier gas N₂ flows into the second carrier gas supply pipe 47.Then, the carrier gas flows from the second carrier gas supply pipe 47,and the flowrate thereof is adjusted to a set value, which is set by thecontroller 57, by the third mass flow controller 48. Also, O₃ gas flowsfrom the second gas supply pipe 34, the flowrate thereof is adjusted bythe third mass flow controller 48, the O₃ gas is mixed with the carriergas whose a flowrate is adjusted together, and the mixture is suppliedinto the process chamber 31 from the second gas supply hole 52 while itis exhausted from the gas exhaust pipe 53.

At this time, by appropriately adjusting the APC valve 54, the inside ofthe process chamber 31 is maintained at a pressure in the range of 10 Pato 900 Pa, for example, 66 Pa. The wafers 2 are exposed to the O₃ gasfor 1 second to 300 seconds. Also, the temperature of the heater 26 isset so that the wafer temperature is in a range of 150° C. to 250° C.,for example, 220° C. as in the supply operation of the TEMAZ gas inSTEP: 01. By supplying the O₃ gas, the O₃ gas and the TEMAZ gas which ischemically adsorbed on the surfaces of the wafers 2 react with eachother, and the ZrO₂ film is formed on each of the wafers 2.

STEP: 04

After the ZrO₂ film is formed, the second valve 46 and the fourth valveare closed, and the inside of the process chamber 31 is vacuum-evacuatedby the vacuum pump 55, and the remaining O₃ gas after the film formationis eliminated. At this time, when an inert gas such as N₂ and the likeis supplied into the reaction tube 27, the effect for eliminating theremaining O₃ gas after the film formation from the process chamber 31may be further enhanced.

The above-described STEP: 01 to STEP: 04 are defined as one cycle, andwhen this cycle is repeated a plurality of times, the ZrO2 films havinga predetermined film thickness may be formed on the wafers 2.

When the film forming process for forming the ZrO₂ film having apredetermined thickness is performed, the inert gas such as N₂ gas andthe like is supplied to the inside of the process chamber 31 and isexhausted from the inside of the process chamber 31 so as to purge theinside of the process chamber 31 by the inert gas (gas purge).Thereafter, the inside of the process chamber 31 returns to atmosphericpressure (return to atmospheric pressure).

After the inside of the process chamber 31 returns to atmosphericpressure, the seal cap 24 is moved downward by the boat elevator 22 soas to open the lower end of the manifold 28 and unload the boat 18 inwhich the processed wafers 2 are supported from the inside of theprocess chamber 31 (boat unloading). Finally, the processed wafers 2 aredischarged from the boat 18 (wafer discharging) so as to complete aseries of processes.

Next, with reference to FIG. 4, in the substrate processing apparatus 1of the present invention, a schematic configuration of a supply/exhaustsystem of a liquid source and solvent will be described.

The supply/exhaust system includes a liquid source tank 59 containingTEMAZ, a solvent tank 61 containing a solvent such as n-Hexane which hasa relatively high vapor pressure when compared to the TEMAZ and does notreact with the TEMAZ, the liquid mass flow controller 35 adjusting aflowrate of the TEMAZ or solvent, the vaporizer 36 vaporizing the TEMAZ,and the vacuum pump 55 exhausting the remaining TEMAZ. The liquid sourcetank 59, the solvent tank 61, the liquid mass flow controller 35, thevaporizer 36, and the vacuum pump 55 are connected to each other bypipes.

Also, the vaporizer 36 is connected to the process chamber 31 (notshown) by disposing a pipe therebetween, and simultaneously, the liquidsource tank 59 and the solvent tank 61 are connected to each other bydisposing a pressurizing inert gas supply system (not shown anddescribed) which supplies pressurizing inert gas such as N₂ and a pipe(not shown and described) therebetween. Thus, the liquid source tank 59and the pressurizing inert gas supply system constitute a liquid sourcesupply system, and the solvent tank 61 and the pressurizing inert gassupply system constitute a solvent supply system.

Also, in the pipe, valves a to j are installed at predetermined parts,and the valves a to j are electrically connected to the controller 57 sothat a passage of the liquid source or solvent flowing into the pipe canbe changed according to a command of the controller 57.

The flowrate control of the liquid source and solvent is performed bythe pressurizing inert gas supplied from the pressurizing inert gassupply system (not shown), and the liquid mass flow controller 35 may beused as a liquid flowmeter which detects only the flowrate of theliquid.

In the current embodiment, in case where the liquid mass flow controller35 is firstly used due to the replacement of the device, actually, forconfirming an operation of the liquid mass flow controller 35 before thefilm forming process is performed, a process for confirming whether theliquid mass flow controller 35 is defective is executed.

Hereinafter, with referent to a flow chart illustrated in FIG. 5, aprocess for confirming the liquid mass flow controller 35 will bedescribed.

STEP: 11

When operation confirmation processing starts by a command transmittedfrom the controller 57, the controller 57 operates the vacuum pump 55first, and the valves c and e are opened so as to depressurize theinside of the pipe in a region surrounded by the valves b, d, f, and jand the vacuum pump 55.

STEP: 12

When the depressurization of the inside of the pipe is completed, thevalves c and e are closed, and the valve a is opened to supply thepressurizing inert gas into the solvent tank 61 so as to boost apressure inside the solvent tank 61.

STEP: 13

After the pressure inside the solvent tank is boosted, the valves b, c,and e are opened, and a flowrate set valve (threshold) of the liquidmass flow controller 35 is inputted from the controller 57. Then, thesolvent is supplied from the solvent tank 61 to the liquid mass flowcontroller 35 by disposing the valves b and c therebetween, and thesolvent supplied into the liquid mass flow controller 35 is exhausted tothe outside of the substrate processing apparatus 1 by disposing thevalve e and the vacuum pump 55 therebetween.

STEP: 14

At this time, the solvent flowrate controlled by the liquid mass flowcontroller 35 is fed back to the controller 57, and the controller 57compares the feed back value to the preset value (for example, 0.5 g) todetermine whether the solvent flows according to the preset value.Whether the solvent flows actually into the liquid mass flow controller35 or whether the solvent flowrate can be controlled is confirmed, andwhen it is determined that the liquid mass flow controller 35 isnormally operated, the solvent is removed. Then, by appropriatelyadjusting the supply and vacuum exhaust of the inert gas such as N₂, theinside of the process chamber 31 is purged, and also, by supplying theliquid source into the liquid mass flow controller 35, the film formingprocessing of the wafers 2 is performed.

Also, when it is determined that the solvent does not flow according tothe preset value, the solvent flowrate cannot be controlled, and theliquid mass flow controller 35 is defective, the film forming processingis stopped. Then, replacement and repair works of the liquid mass flowcontroller 35 are performed.

Also, the operation of the liquid mass flow controller 35 may bedirectly confirmed by a worker through a screen of the controller 57, ormay be confirmed by the controller 57. In addition, an alarming part(not shown) is added to the controller 57, and in case where the liquidmass flow controller 35 is abnormally operated, by informing an alarmmessage such as generation of sound by the alarming part, display on thescreen, or lighting of an alarm light such as a patrol car light to theworker, its purpose may be notified.

When the film forming of the wafers 2 is performed, the liquid sourceinside the liquid source tank 59 is transferred to the vaporizer 36 viathe liquid mss flow controller 35, and then, after the liquid source isvaporized by the vaporizer 36, the liquid source is supplied into theprocess chamber 31 by disposing the valve h therebetween so as tocontribute the film forming of the wafers 2. After the films are formedon the wafers 2, the vaporizer liquid source is exhausted from the gasexhaust pipe 53 by disposing the vacuum pump 55 therebetween.

When the film forming process is formed for a predetermined time,by-products are generated within the vaporizer 36. At this time, thesolvent inside the solvent tank 61 may be used as a cleaning solutionfor cleaning the inside of the vaporization 36.

When the cleaning process is performed, according to a commandtransmitted from the controller 57, all of the valves a to j are closed,and then, the valves e and f are opened. The liquid source remainingwithin the pipe in a region surrounded by the valves c, d, g, h, and jis exhausted by disposing the vacuum pump 55 so as to make the inside ofthe pipe in a vacuum state.

Next, by opening the valve j, the inside of the pipe is purged by thepressurizing inert gas, and then, the purge process is finished. Then,the valve j is closed to make the inside of the pipe in the vacuumstate.

Next, the valves a and b are opened, and the solvent is introduced intothe vaporizer 36 by the effect of the pressurizing inert gas. After apredetermined time elapses, by closing the valves a and b and openingthe valves g and j, the by-products within the vaporizer 36 may beremoved. Finally, by closing the valves g and j and opening the valves eand f, the inside of the pipe may be depressurized and the solventremaining in the pipe may be removed. At this time, since the materialremaining in the pipe is a high volatile solvent such as n-Hexane andthe like, even though the solvent remaining in the pipe is notcompletely removed only by the purge using the pressurizing inert gasand the decompression using the vacuum pump 55, the solvent isvaporized, and thus does not remain in the pipe.

As described above, using the high volatile solvent which does notremain in the pipe, since the operation of the liquid mass flowcontroller 35 or the liquid flowmeter is confirmed before the filmforming processing, the processes such as the liquid removal process→thepurge process→the cleaning process using the solvent→the purge process,which are required when the defects of the liquid mass flow controller35 or the liquid flowmeter are detected are unnecessary during the filmforming processing. Thus, the work time may be significantly reduced,and simultaneously, it may prevent members such as the pipe from beingcontaminated by reaction between the residual liquid source and theatmosphere during the replacement works.

Also, since the pipe and the vaporizer 36 may be cleaned using thesolvent, a system for supplying a new cleaning solution is not required,and thus, manufacturing costs may be reduced.

In the current embodiment, the operation confirmation of the liquid massflow controller 35 is mainly performed when initially adjusted.Particularly, in the film forming process (for example, high-k filmforming process) which cannot be stopped when once the liquid sourceflows, the operation confirmation is not performed in timing except theinitial adjustment. In the film forming process, the supply of theliquid source corresponds to the operation confirmation of the liquidmass flow controller 35, and in the step in which the defects of theliquid mass flow controller 35 are detected, the processing is stopped,and then, the liquid mass flow controller 35 is replaced.

Also, the present invention is not limited to the ZrO₂ film forming, andas a kind of films formed using a liquid source having a low vaporpressure, the present invention can be applied to other kinds of filmsformed using the vaporizer and the mass flow controller.

According to the conditions of applicable solvent, organic solventshaving a vapor pressure greater than that of the liquid source can beapplied, and preferably, high volatile solvents can be applied. Thecombination of the solvents can be changed by kinds of the liquidsource. For example, in relation to TEMAZ and TEMAH, material such asoctane having the different number of atoms of carbon can be applied,and also, material such as hexane containing six carbon atoms in achain, haxtane containing seven carbon atoms in a chain, and octanecontaining eight carbon atoms in a chain can be applied.

According to the present invention, the substrate processing apparatusincludes: a process chamber receiving a substrate; a liquid sourcesupply system supplying a liquid source which is a liquid at roomtemperature and atmospheric pressure into the process chamber; a solventsupply system supplying a solvent having a vapor pressure greater thanthat of the liquid source into the process chamber; a liquid flowratecontrol device controlling flowrates of the liquid source and thesolvent; and a controller controlling the liquid source supply system,the solvent supply system, and the liquid flowrate control device. Here,the controller controls the liquid source supply system, the solventsupply system, and the liquid flowrate control device so that thesolvent is supplied into the liquid flowrate control device than thesolvent supply system to confirm an operation of the liquid flowratecontrol device before the liquid source supply system supplies theliquid source into the process chamber by disposing the liquid flowratecontrol device therebetween. Thus, the processes required when defectsof the liquid flowrate control device are detected or the liquidflowrate control device is replaced can be significantly reduced, andsimultaneously, the contamination due to the reaction between theresidual source and the atmosphere during the replacement works can beprevented.

According to the present invention, the substrate processing apparatusis configured to supply the liquid source into the process chamber toform a film on the substrate, and the controller includes: a measuringpart monitoring the liquid flowrate control device to measure a flowrateof the solvent flowing into the liquid flowrate control device; and acomparing part comparing the measured flowrate of the solvent to apredetermined threshold value. Here, when the flowrate of the solvent isin a range of the predetermined threshold value, the solvent is removedfrom the process chamber, and the liquid source is supplied to form thefilm on the substrate. Thus, it can prevent the liquid source fromflowing in a state where the defects of the liquid flowrate controldevice occur, and also prevent time and labor required during thereplacement works from being increased.

According to the present invention, the substrate processing apparatusincludes: a process chamber receiving a substrate; a source supplysystem supplying a vaporized gas formed by vaporizing a liquid sourcewhich is a liquid at room temperature and atmospheric pressure using avaporizer into the process chamber; a reaction gas supply systemsupplying an reaction gas reacting with the vaporized gas into theprocess chamber; a solvent supply system supplying a solvent having avapor pressure greater than that of the vaporized gas into the processchamber; a liquid flowrate control device controlling flowrates of theliquid source and the solvent; and a controller controlling the sourcesupply system, the reaction gas supply system, the solvent supplysystem, and the liquid flowrate control device. Here, the controllercontrols the source supply system, the reaction gas supply system, thesolvent supply system, and the liquid flowrate control device so thatthe solvent is supplied into the liquid flowrate control device than thesolvent supply system to confirm an operation of the liquid flowratecontrol device before the source supply system supplies the liquidsource into the process chamber by disposing the liquid flowrate controldevice therebetween. In addition, the controller alternately suppliesthe vaporized gas and the reaction gas after confirming the operation ofthe liquid flowrate control device to form the film on the substrate.Thus, the processes required when the liquid flowrate control device isreplaced can be significantly reduced, and simultaneously, it canprevent the liquid source from flowing in a state where the defects ofthe liquid flowrate control device occur, and also prevent time andlabor required during the replacement works from being increased.

According to the present invention, the method of manufacturing thesemiconductor device includes: supplying a solvent into a liquidflowrate control device connected to a process chamber; monitoring theliquid flowrate control device to measure a flowrate of the solventflowing into the liquid flowrate control device; comparing the measuredflowrate of the solvent to a predetermined threshold value; removing thesolvent from the process chamber when the flowrate of the solvent is ina range of the predetermined threshold value; vaporizing a liquid sourcesupplied by disposing the liquid flowrate control device to supply thevaporized gas into the process chamber; and alternately supplying anreaction gas reacting with the vaporized gas to form a predeterminedfilm on a surface of a substrate placed in the process chamber. Thus,the processes required when the liquid source flows in the state wherethe defects of the liquid flowrate control device occur to replace theliquid flowrate control device can be significantly reduced.

According to the present invention, the method of confirming theoperation of the liquid flowrate control device includes: supplying asolvent into a liquid flowrate control device connected to a processchamber; monitoring the liquid flowrate control device to measure aflowrate of the solvent flowing into the liquid flowrate control device;comparing the measured flowrate of the solvent to a predeterminedthreshold value; and removing the solvent from the process chamber whenthe flowrate of the solvent is in a range of the predetermined thresholdvalue. Thus, the defects of the liquid flowrate control device can beeasily detected, and the processes required when the liquid flowratecontrol device is replaced can be significantly reduced, andsimultaneously, the contamination due to the reaction between theresidual source and the atmosphere during the replacement works can beprevented.

Supplementary Note

The present invention also includes the following embodiments.

Supplementary Note 1

According to an embodiment of the present invention, there is provided asubstrate processing apparatus comprising:

-   a process chamber accommodating a substrate;-   a liquid source supply system supplying a liquid source which is a    liquid at room temperature and atmospheric pressure into the process    chamber;-   a solvent supply system supplying a solvent having a vapor pressure    greater than that of the liquid source into the process chamber;-   a liquid flowrate control device controlling flowrates of the liquid    source and the solvent; and-   a controller controlling the liquid source supply system, the    solvent supply system, and the liquid flowrate control device,-   wherein the controller controls the liquid source supply system, the    solvent supply system, and the liquid flowrate control device so    that the solvent is supplied into the liquid flowrate control device    than the solvent supply system to confirm an operation of the liquid    flowrate control device before the liquid source supply system    supplies the liquid source into the process chamber by disposing the    liquid flowrate control device therebetween.

Supplementary Note 2

The substrate processing apparatus may be configured to supply theliquid source into the process chamber to form a film on the substrate,and

-   the controller may comprise:-   a measuring part monitoring the liquid flowrate control device to    measure a flowrate of the solvent flowing into the liquid flowrate    control device; and-   a comparing part comparing the measured flowrate of the solvent to a    predetermined threshold value,-   wherein, when the flowrate of the solvent is in a range of the    predetermined threshold value, the solvent may be removed from the    process chamber, and the liquid source may be supplied to form the    film on the substrate of Supplementary Note 1.

Supplementary Note 3

In the substrate processing apparatus of Supplementary Note 2, when theflowrate of the solvent is out of the range of the predeterminedthreshold value, the solvent may be removed from the process chamber,and maintenance of the flowrate control device may be performed.

Supplementary Note 4

In the substrate processing apparatus of Supplementary Note 2, thecontrol may comprise an alarming part and inform an alarm messagethrough the alarming part when the flowrate of the solvent is out of therange of the predetermined threshold value.

Supplementary Note 5

In the substrate processing apparatus of Supplementary Note 4, the alarmmessage may comprise one of sound, display on a screen, and lighting ofan alarm light.

Supplementary Note 6

In the substrate processing apparatus of Supplementary Note 1, theoperation confirmation of the liquid flowrate control device may beperformed when initially adjusted or the liquid flowrate control deviceis replaced.

Supplementary Note 7

According to another preferred embodiment of the present invention,there is provided a method of manufacturing a semiconductor device, themethod comprising:

-   supplying a solvent into a liquid flowrate control device connected    to a process chamber;-   monitoring the liquid flowrate control device to measure a flowrate    of the solvent flowing into the liquid flowrate control device;-   comparing the measured flowrate of the solvent to a predetermined    threshold value;-   removing the solvent from the process chamber when the flowrate of    the solvent is in a range of the predetermined threshold value;-   vaporizing a liquid source supplied by disposing the liquid flowrate    control device to supply the vaporized gas into the process chamber;    and-   alternately supplying an reaction gas reacting with the vaporized    gas to form a predetermined film on a surface of a substrate placed    in the process chamber.

Supplementary Note 8

According to another preferred embodiment of the present invention,there is provided a method of confirming an operation of a liquidflowrate control device, the method comprising:

-   supplying a solvent into a liquid flowrate control device connected    to a process chamber;-   monitoring the liquid flowrate control device to measure a flowrate    of the solvent flowing into the liquid flowrate control device;-   comparing the measured flowrate of the solvent to a predetermined    threshold value; and-   removing the solvent from the process chamber when the flowrate of    the solvent is in a range of the predetermined threshold value.

1. A substrate processing apparatus comprising: a process chamberaccommodating a substrate; a liquid source supply system supplying aliquid source into the process chamber, the liquid source being at aliquid state at room temperature and under atmospheric pressure; asolvent supply system supplying a solvent into the process chamber, thesolvent having a vapor pressure greater than that of the liquid source;a liquid flowrate control device controlling flowrates of the liquidsource and the solvent; and a controller controlling the liquid sourcesupply system, the solvent supply system, and the liquid flowratecontrol device, wherein the controller controls the liquid source supplysystem, the solvent supply system, and the liquid flowrate controldevice in a manner that the solvent is supplied to the liquid flowratecontrol device to check an operation of the liquid flowrate controldevice before the liquid source supply system supplies the liquid sourceinto the process chamber via the liquid flowrate control device.
 2. Thesubstrate processing apparatus of claim 1, wherein the liquid source issupplied into the process chamber to form a film on the substrate, andthe controller comprises: a measuring part monitoring the liquidflowrate control device to measure a flowrate of the solvent flowinginto the liquid flowrate control device; and a comparing part comparingthe measured flowrate of the solvent to a threshold value, wherein thesolvent is removed from the process chamber and the liquid source issupplied to form the film on the substrate when the flowrate of thesolvent is within a range of the threshold value.
 3. The substrateprocessing apparatus of claim 2, wherein the solvent is removed from theprocess chamber and a maintenance of the flowrate control device isperformed when the flowrate of the solvent is out of the range of thethreshold value.
 4. The substrate processing apparatus of claim 2,wherein the controller further comprises: an alarming part to issue analarm message when the flowrate of the solvent is out of the range ofthe threshold value.
 5. The substrate processing apparatus of claim 4,wherein the alarm message comprises one of a sound, a display on ascreen, and a lighting of an alarm light.
 6. The substrate processingapparatus of claim 1, wherein the operation of the liquid flowratecontrol device is checked during an initial adjustment or at areplacement of the liquid flowrate control device.
 7. A method ofconfirming an operation of a liquid flowrate control device, the methodcomprising: supplying a solvent into a liquid flowrate control deviceconnected to a process chamber; monitoring the liquid flowrate controldevice to measure a flowrate of the solvent flowing into the liquidflowrate control device; comparing the measured flowrate of the solventto a threshold value; and removing the solvent from the process chamberwhen the flowrate of the solvent is within a range of the thresholdvalue.